Selected optimization data for the carbonyl fluoromethylative amination reaction.

Entry	Initiation method	HAT reagent	Additive	Yielda (%)
1	40 W blue LED	(Me3Si)3Si–H	—	<5
2	40 W blue LED	(Me3Si)3Si–H	TMS–Cl	30
3	40 W blue LED	(Me3Si)3Si–H	TMS–OTf	94
4	40 W blue LED	(Me3Si)3Si–H	TBS–OTf	95 (86)
5	50 °C, air atm	(Me3Si)3Si–H	TBS–OTf	0
6	70 °C, AIBN	(Me3Si)3Si–H	TBS–OTf	77
7	70 °C, AIBN	Bu3Sn–H	TBS–OTf	0
8	40 W blue LED	(Et3Si)3Si–H	TBS–OTf	52
9	40 W blue LED	Et3Si–H	TBS–OTf	0
10	40 W blue LED	Ph3Si–H	TBS–OTf	0
11	40 W blue LED	PhSiH3	TBS–OTf	0

^aYields determined by ¹H NMR analysis using 1,1,2,2-tetrachloroethane as internal standard. Isolated yield given in parentheses.